Diffusion isolation layer for maskless cladding process

ABSTRACT

In a maskless metal cladding process for plating an existing metallurgical pattern, a protective layer is utilized to isolate those areas of underlying metallurgy on which additional metal plating is not desired. The layer acts as an isolation barrier to protect the underlying metallurgy from deposition and subsequent diffusion of the heavy metal overlay. The composition of the protective layer is selected as one having sufficient mechanical integrity to withstand process handling and support the gold overlay and having the thermal integrity to withstand the high temperatures reached during metal sputtering and diffusion processes. The isolation barrier layer has an organic component as a binder which thermally decomposes, either in a heating step before metal deposition or during the diffusion cycle, leaving no carbonaceous residue but leaving an inert, inorganic standoff to support the metal. After diffusion of the metal, the remaining inorganic standoff layer, overlying metal and any undiffused metal remaining on the non-patterned substrate is easily removed by a standard technique, such as ultrasonics.

This is a divisional of application Ser. No. 666,954 filed Oct. 30,1984, now U.S. Pat. No. 4,582,722.

The subject invention relates to a method of depositing metal layers onto an existing metallurgy pattern on a supporting dielectric substrate.More particularly, it relates to coating metal on selected metalconductive patterns while leaving other metallurgy uncoated; all of saidmetal patterns being found on ceramic substrate carriers of the typeemployed for mounting semiconductor devices.

BACKGROUND OF THE INVENTION

The steps for fabricating multi-layer ceramic substrates for integratedcircuit package assemblies are well-known. Generally, a paste or slurryis prepared combining ceramic particulates (e.g. alumina), a binder andsolvent therefor. The paste is cast or doctor bladed into sheets whichare then dried and sized. The dried sheets are subsequently punched toform via holes; and screened to provide metallurgy to fill the viaholes. The sheets are then stacked, laminated and sintered. The sinteredsubstrates can be employed for mounting semiconductor devices which areelectrically connected to the internal circuitry of the substrate.

Electrical connection from an external power source to the internalcircuitry of the substrate is made through input/output, I/O, pinsmounted on the bottom of the substrate. Electrical connection on the topof the substrate must be made to the integrated circuit devices andamong engineering change, EC, pads. It is necessary, therefore, toprovide a relatively complex metallurgy to the substrate.

On the top surface of the substrate, there may be dozens of EC padsalong with I/O pad patterns designated for mounting, perhaps, nineintegrated circuit "chips". The chip mounting is generally done using a"flip-chip" orientation whereby the chips are mounted to the I/O pads onthe substrate surface using a solder reflow or similar standard process.In order to achieve a good bond for the lead-tin solder, the chipmounting, I/O pad is frequently prepared with a thin coat of gold on athin coat of nickel deposited over the molybdenum via metallurgy. U.S.patent application Ser. No. 359,469 of A. H. Kumar et al, assigned toassignee of the present invention, discusses a two-materialmetallization process applied to both the I/O and EC pads. Thoseteachings are herein incorporated by reference. As discussed therein,nickel has excellent adhesion to molybdenum and the subsequent thinflash layer of gold prevents oxidation of the nickel. In addition, thevery thin coating of gold on the I/O pads allows for a good solder bondfor chip mounting. A heavy concentration of gold on the I/O pads,however, could contaminate the lead-tin solder and result in pooradhesion. The nickel and gold-treated EC pads, on the other hand,require additional heavy plating with gold to allow for frequent andrepeated changes in the wire bonding to the pads thereby accommodatingtesting, engineering changes and defect compensation.

The need to plate the conductive pad patterns, EC and I/O, differentlyis discussed in patent application Ser. No. 560,661, filed 12/12/83, nowU.S. Pat. No. 4,526,859, of Christensen, et al, assigned to the assigneeof the present invention and herein incorporated by reference. There,the use of photoresists as masking layers is discussed for use inobtaining a heavy metal, for example gold, coating on either only the ECpads or only the I/O pads. The use of resists as masks is well-known, asevidenced by the teachings in Japanese application No. 50-124930,publication No. 52-48992, Apr. 19, 1977 and in U.S. Pat. No. 3,957,552of Ahn, et al. As in Christensen, et al, the references teach theapplication of a resist, selective exposure of the resist using anappropriate mask and development of the exposed resist forming a patternand revealing the underlying surface intended to be metallized.Metallization of the entire surface follows whereby the metal layer isdeposited on the unexposed resist and on the patterned underlyingsurface. Removal by float-away or etching techniques of the remainingresist with overlying metal results in a clean, metal-patterned surface.

Similarly, metal masks can be used by placing them in registration withthe substrate and, essentially, screening through the mask. It isfrequently difficult however to achieve registration of a pre-formedmetal mask with a substrate which has undergone uneven shrinkage duringsintering.

The method of depositing the metal may be one of many well-knowntechniques. The Christensen, et al reference utilizes dry depositionprocesses such as magnetron sputtering or ion plating, in gross, withphotoresists in place. Indiscriminate deposition of metal over theentire surface may also be obtained by painting the metal (See: U.S.Pat. No. 3,741,735, Buttle), dipping the article in molten metal (See:U.S. Pat. No. 2,788,289 to Double), sputtering, evaporation techniquesor vapor deposition (all well-known methods cited in U.S. Pat. No.4,293,587 of Trueblood). In all of these processes, a subsequent resistpatterning and metal etching step is required to remove excess metalfrom the substrate. Electroplating, such as is seen in IBM TechnicalDisclosure Bulletin, Vol. 22 No. 4, Sept. '79, page 1439 by Kowalczyk,is a metal deposition method which can insure specific application ofoverlying metal to the intended metal pattern by providing a conductivepath to only those pads to be plated. Another known method of depositionrequiring no masking step is the maskless cladding process described inU.S. Pat. No. 4,442,137 to Kumar. Therein, a blanket metal coating isdeposited, by sputtering, vapor deposition or other known process, andsubsequently heated to a temperature sufficient to cause the overlying,e.g. gold, coat to diffuse with the underlying metallurgy. At the sametime as the metal-to-metal diffusion is occurring, the varying shrinkagerates of the substrate material and the overlying metal produce stressessufficient to cause the metal deposited on the substrate to flake orspall and consequently be readily removable in a follow-up mechanicalcleaning step, such as ultrasonic removal of the residue.

The deposition and diffusion, however, is nonselective and thereforecauses the heavy overlying metal to diffuse and adhere to all of themetal interconnection pads, EC and I/O alike. As noted above, it isdesirable to have a thick gold coating on the EC pads but not on theI/O, chip mounting, pads.

It is therefore an object of the present invention to provide a methodfor depositing metal onto a selected portion of a metallurgical pattern.

It is another object of the invention to provide an isolation barrieragainst metal deposition to a selected portion of a metallurgicalpattern.

It is a further object of the invention to provide an isolation barrierfor use in a maskless cladding operation.

It is still another object to provide an isolation barrier having thethermal integrity to withstand metal deposition temperatures and themechanical and thermal integrity to support a metal overlay film duringsubsequent diffusion steps.

It is a final object to provide a substrate isolation barrier having thethermal and mechanical integrity to withstand necessary processing andbeing readily removable leaving no residue on the substrate.

SUMMARY OF THE INVENTION

These and other objects are achieved by the subject invention wherein aselected portion of the metallurgical pattern on a dielectric substrateis isolated from subsequent processing by a screened barrier layercomprised of a ceramic particulate paste having a polymer binder and alow vapor pressure solvent. The barrier layer is allowed to dry to expelthe solvent and is baked in a reducing atmosphere to expel the polymerbinder. The remaining inorganic layer, having no organic or carbonaceousresidues, has sufficient strength to withstand the subsequent masklesscladding processing steps of metal deposition, diffusion and patterningto remove the metal from the non-metallic substrate areas. During"patterning", the barrier layer is also removed leaving a clean,selectively metallized surface.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be detailed in the accompanying specification anddrawings wherein:

FIGS. 1A, B, C and D illustrate in substrate cut-away cross-section theprocessing steps involved in utilizing the subject invention.

FIG. 2 is a top view of a substrate to be metallized.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The basic processing steps for a multilayer ceramic (MLC) structure arewell-known and can be found in U.S. Pat. No. 3,518,756 of Bennett, etal. As illustrated in FIGS. 1 and 2, a processed, sintered MLC substratebears patterns of exposed metallurgy on its surface. The subjectinvention relates to plating/metallizing the exposed metal of thepatterns of metallurgy found on the substrate. The pattern of metallurgyconcerned may be solely on one surface of the substrate, may be found onseveral surfaces and/or may penetrate many layers of the structure. TheFigures illustrate in top view and in cut-away cross-section, only thesurface of the metallurgy and the substrate, which are the objects ofthis invention. Substrate 12, as noted above, may contain severalpatterns of metallurgical features serving differing purposes.

In multi-layer ceramics, the metallurgical pattern on the surface iscreated from the via formation and screening steps and is generally amolybdenum-based metallurgy. Molybdenum does not, traditionally, providethe best adhesion qualities for soldered or brazed electricalconnection. In addition, the molybdenum will oxidize the undergoreactive corrosion when exposed to humidity if not provided with aprotective coating. Therefore, the molybdenum metallurgical pads are"pretreated" as is described by Kumar, et al in patent application Ser.No. 359,469 assigned to assignee of the present invention and hereinincorporated by reference. Kumar, et al teaches the deposition of, forexample, nickel, a metal having excellent adhesion characteristics withmolybdenum, then a thin flash gold layer to prevent oxidation of thenickel. The Ni-Au treatment of all of the metallurgy pads provides boththe protection and brazeable/solderable characteristics desired.

The pattern of metallurgy 13 found at locations 14 is that metal towhich the integrated circuit chips will be connected, referred to aschip mounting or I/O pads. The I/O pads bear the very thin coating ofprotective ad conductive metal discussed above. The thin gold isnecessary on the I/O pads for mounting the chips to the existingmetallurgy by solder bonding. The other metallurgical pattern, comprisesthe engineering change, EC, pads, 15, associated with the substrate. TheEC pads provide alternate electrical pathways to the I/O metallurgy andthe substrate by the application thereto of interconnecting wires toaccommodate engineering changes, testing and defect correction. Giventhe repeated uses envisioned for any one EC pad, it is preferred that anadditional heavy layer of gold be associated with the EC pads.

For application of the metal to the pads alone, without concurrentlycoating the substrate, masks have been utilized. The difficulty in usingmasks is that the non-uniform shrinkage of the substrate duringsintering makes it virtually impossible to achieve registration of amask with the sintered substrate.

Selective plating by electroplating may also be employed; but, it issomewhat limited in its applicability to EC pads since EC pads arefrequently "floating" and cannot therefore be electrically connected forthe electroplating process.

Metallization by the use of diffusion techniques as described in U.S.Pat. No. 4,442,137 of Kumar, can assure that each pad is adequatelycoated while metal deposited on the surrounding substrate area is easilyand properly removed. The metal is applied to the entire patternedsubstrate surface, as by sputtering or vapor deposition. Themetal-coated substrate is then heated to a temperature sufficient todiffuse the metal into the underlying pattern. Given the differingthermal contraction properties of the overlying metal and the substrateduring the diffusion-heating step, the metal which is overlyingnon-patterned areas is caused to flake or spall and consequently iseasily removed from the now metallized patterned substrate. Thismaskless cladding process avoids the difficulties of correct maskregistration and repeated depositing, masking, and etching steps. Thedrawback to the process heretofore has been that the cladding processinvolves the entire substrate and therefore coats all metallurgy withthe same materials and the same layer thicknesses. Such a scheme ishighly useful for the preliminary preparation of the metallurgy, as wasnoted in Kumar No. 359,469 above, whereby every metallurgical pad iscoated with a thin nickel and thin gold layer to enhance the pad'sadhesive qualities. It is, however, of little utility for selectivelyapplying an additional heavy metal layer to the EC pads, but not to theI/O pads.

The use of a mask to shield the I/O pads from metallization would appearto be a workable solution; however, no presently known mask can providethe requisite qualities to withstand the maskless cladding process. Ametal mask, again, has the problem of alignment and registration with asintered, cambered substrate. Resists such as well-known photoresists orE-beam resists cannot survive the deposition, e.g. sputtering,temperatures. Common lithographic materials degrade or shrivel at theprocessing temperatures of >250° C. reached during, for example,sputtering, and thereby fail to effectively shield the masked areas fromgold deposition. In addition, most photoresists will char when heated,during the diffusion step, to above 400° C. in a reducing atmosphere.Removal of the char, or carbonaceous residue, would require additionalprocessing steps, such as prolonged plasma ashing. The resists would,during the diffusion step, undoubtedly collapse and result incontamination of the underlying "protected" layer.

There is herein disclosed a suitable masking material enabling one toprovide an isolation barrier over the I/O pads while depositing heavygold on the EC pads and substrate using a maskless cladding process. Apaste is formulated of alumina including a depolymerizable polymerbinder and a solvent. The paste is screened, sprayed or otherwiseselectively deposited onto the area to be protected, as illustrated inFIG. 1B at reference numeral 16. The polymer binder enables the paste tobe readily applied and to adhere to the surface of the substrate and/ormetallurgy to be protected. After screening, the paste is allowed to dryat room temperature to expel the solvent, followed by an accelerateddrying step to drive off the polymer binder by "unzipping", ordepolymerizing, the same. What remains is a durable inorganic barrierlayer, 16'. The heavy metal deposition may now be performed using vapordeposition, sputtering or other known technique resulting in acontinuous coating 17 over the entire substrate 12, including themetallurgy intended to be plated, here the EC pads 15 of FIG. 1C, theexposed substrate surface, and the protective coating 16'. Subsequentdiffusion processing may proceed in the established manner, found in theKumar U.S. Pat. No. 4,442,137. The isolation barrier layer, 16', hasboth the mechanical and thermal integrity to withstand the weight of thethick metal layer and the temperatures achieved for diffusing the metallayer to the underlying metallurgy and debonding it with the substrate.After the diffusion process is completed, the substrate is "patterned"in accordance with Kumar's teachings of U.S. Pat. No. 4,442,137. The"patterning", for example by ultrasonic horn exposure, results in theremoval of the debonded or spalled metal found on the adjacent baresubstrate surface, removes the overlying metal in the shielded area andalso effects the removal of the inorganic barrier layer 16'. The result,as intended, is a clean substrate having selectively coatedmetallurgical patterns prepared for chip mounting and further connectionand use.

The formulation of the isolation barrier material comprises a uniquecombination of ingredients to yield the thermal and mechanicalcharacteristics desired. The inorganic base of ceramic, for examplealumina or glass ceramic, must, once solvents and binders are removed,be solid and impermeable enough to support the gold or other metal layeraway from the underlying protected metallurgy. The inorganic ceramiccannot effectively be deposited directly on the substrate so thedepolymerizable polymer binder and solvent are mixed to form thescreenable, sprayable or otherwise applicable paste. A low vaporpressure solvent, such as amylacetate, is recommended for use if thebarrier material is to be applied by screening. A more volatile solventwould clog the screens during application. The polymer binder must beone of a group which is readily decomposable at a known temperature soas to depolymerize leaving no carbonaceous residue on the substrate oron the barrier layer. Examples, though not an exhaustive list ofsuitable polymers, include polymethylmethacrylate and othermethylmethacrylates, acrylates and copolymers; polyalphamethylstyrene;polyisobutylene; and low temperature decomposing nitrocellulose orpolyphthalaldehyde. As noted above, a step may be taken to heat theapplied barrier layer in order to depolymerize the polymer, essentiallypurging the inorganic layer before metal deposition. It is, however,possible to forego that heating step. The polymer chosen, such aspolymethylmethacrylate, may decompose during the diffusion step at thediffusion temperatures of 350° C.-450° C., serving the same function andleaving the organic-free ceramic particulate structure to support theheavy metal layer and isolate the underlying metallurgy. A suitablesample formulation consists of

polymethylmethacrylate 6.58%

amylacetate 26.33%

alumina powder 65.83%

fumed silica 1.25%

The foregoing invention has been described with reference to a preferredembodiment. It will be understood, however, that modifications in detailmay be made without departing from the spirit and scope of the inventionas hereinafter claimed:

What is claimed is:
 1. A diffusion barrier material having sufficientthermal and mechanical integrity to protect selected metal areas of aplurality of spaced metal areas on the surface of a substrate duringmaskless cladding consisting essentially of: polymethylmethacrylate,amylacetate, and a ceramic particle base comprising alumina powder andfumed silica, wherein said material has sufficient thermal andmechanical integrity to protect selected metal areas of a plurality ofspaced metal areas on the surface of a substrate during masklesscladding.
 2. A screenable paste to protect selected metal areas of aplurality of spaced metal areas on an alumina ceramic substrate surfaceduring maskless cladding comprising:polymethylmethacrylate, amylacetateand a ceramic particle base comprising alumina powder and fumed silicawherein said paste protects selected metal areas of a plurality ofspaced metal areas on an alumina ceramic substrate surface duringmaskless cladding.
 3. The barrier material of claim 1 wherein theceramic particle base comprises a majority component of said material.4. The paste of claim 2 wherein the ceramic particle base comprises amajority component of said paste.